JPH0228592B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 5-haloorotic acids, which are new compounds, and a method for producing the same. More specifically, the invention provides the formula [In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an allyl group, a cyclohexyl group, a benzyl group, or

[Formula] (wherein R ² represents a methyl group, methoxy group or a halogen atom, n is 0, 1 or 2), and X is chlorine, bromine or iodine] 5-haloorotic acids, and the formula (wherein Me represents an alkali metal and R ¹ has the same meaning as above) and a halogenating agent are reacted. This is a method for producing 5-haloorotic acids represented by the formula (wherein R ¹ and X each have the same meanings as above). The 5-haloorotic acids represented by the formula [] are new compounds and are useful as medicines, agricultural chemicals, and intermediates thereof, particularly as agricultural chemicals against cucumber powdery mildew. Specific examples of the alkali metal salt of 5-carboxyorotate represented by the formula [] include 5-carboxy-1-propylorotate potassium salt, 1-
Butyl-5-carboxyorotate potassium salt,
1-Butyl-5-carboxyorotate sodium salt, 1-butyl-5-carboxyorotate lithium salt, 1-allyl-5-carboxyorotate potassium salt, 5-carboxy-1-cyclohexyl orotate potassium salt, 5- Carboxy-1
-Cyclohexylorotate sodium salt, 1-
Benzyl-5-carboxyorotate potassium salt, 5-carboxy-1-phenylorotate potassium salt, 5-carboxy-1-phenylorotate sodium salt, 5-carboxy-1-phenylorotate lithium salt, 5-carboxy-1-
Tolyrotate potassium salt, 5-carboxy-
1-Tolyrotate sodium salt, 5-carboxy-1-tolyrotate lithium salt, 5-carboxy-1-(chlorophenyl)orotate sodium salt, 5-carboxy-1-(dichlorophenyl)orotate potassium salt, 5- Carboxy-1-(dichlorophenyl)orotate sodium salt, 5-carboxy-1-(dichlorophenyl)orotate lithium salt, 5-carboxy-1
-Methoxyphenylorotic acid sodium salt, etc. Specific examples of halogenating agents include halogens such as chlorine, bromine and iodine, hypohalous acids and their alkali metal salts such as hypochlorous acid, hypobromous acid and hypoiodic acid, and N-chlorosuccinimide. , N-haloyimides such as N-bromosuccinimide and N-bromophthalimide. The amount of the halogenating agent used is preferably 2 to 2.5 mol per 1 mol of the alkali metal salt of 5-carboxyorotic acid. The reaction between the alkali metal salt of 5-carboxyorotic acid and the halogenating agent is preferably carried out using water as a reaction solvent. In some cases, a combination of an inert solvent and water may be used in the reaction of this invention. Examples of inert solvents include benzene,
Examples include chlorobenzene, dichlorobenzene, and carbon tetrachloride. The reaction may be carried out by any method as long as the alkali metal salt of 5-carboxyorotic acid and the halogenating agent can be brought into contact at a predetermined temperature for a predetermined time.
The method of contacting these raw materials is usually to add a halogenating agent directly to an aqueous solution or suspension of an alkali metal 5-carboxyorotic acid salt, or to add the halogenating agent as an aqueous solution or a solution in the above-mentioned inert organic solvent. be done. The reaction between an alkali metal salt of 5-carboxyorotic acid and a halogenating agent improves the yield of the target product, 5-haloorotic acid, by adding an alkali metal hydroxide to the reaction system. It is preferable to add 1 to 3 moles of hydroxide to the reaction system per mole of the alkali metal 5-carboxyorotic acid salt. The alkali metal salt of 5-carboxyorotic acid represented by the formula [] is the formula (In the formula, R ¹ has the same meaning as above, and R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms.) By reacting with alkali hydroxide at room temperature or under heating, the formula (In the formula, R ¹ and Me have the same meanings as above) A method of adding a mineral acid to the reaction product mixture after converting it into a dialkali metal salt of 5-carboxyorotic acid (wherein R 1 and Me have the same meanings as above) Patent application related to 1972-
161384 (see JP-A-57-85375)), this reaction product mixture or the reaction product mixture before mineral acid treatment may be directly subjected to the reaction of the present invention. . If the reaction temperature is too high, the yield of the desired product will decrease, so it is generally preferred that the reaction temperature be in the range of 0 to 100°C. The reaction is usually completed in 1 to 25 hours. The desired product, 5-haloorotic acid, is often a crystal that is difficult to dissolve in water, and can be isolated by filtering the reaction product mixture. When 5-haloorotic acid is dissolved in water, water and solvent are removed from the reaction product mixture by a known method such as distillation, and the 5-haloorotic acid is extracted using an organic solvent. Can be isolated. Furthermore, when the reaction between the alkali metal salt of 5-carboxyorotic acid and the halogenating agent is carried out by adding an alkali metal hydroxide, the reaction product mixture contains an amount of hydrochloric acid equivalent to the alkali metal hydroxide used. , by adding a mineral acid such as sulfuric acid and performing the above operation, 5-
Haloorotic acid can be isolated. 5- expressed by the formula [] obtained by this invention
Specific examples of haloorotic acid include 5-chloro-
1-Propylorotic acid, 5-chloro-1-phenylorotic acid, 5-chloro-1-methoxyphenylorotic acid, 5-chloro-1-(chlorophenyl)orotic acid, 5-bromo-1-propylorotic acid, 5 -Bromo-1-butylorotic acid,
1-benzyl-5-bromoorotic acid, 5-bromo-1-phenylorotic acid, 5-bromo-1-
Tolylorotic acid, 5-bromo-1-methoxyphenyl orotic acid, 5-bromo-1-(chlorophenyl)orotic acid, 5-bromo-1-(dichlorophenyl)orotic acid, 5-iodo-1-propylorotic acid , 1-cyclohexyl-5-iodoorotic acid, 1-allyl-5-iodoorotic acid, 5-iodo-1-phenylorotic acid, 5-
Iodo-1-methoxyphenyl orotic acid, 1-
Examples include (chlorophenyl)-5-iodoorotic acid. Next, examples will be shown. In the examples, the yield of 5-haloorotic acid is the yield based on the alkali metal salt of 5-carboxyorotic acid used. Example 1 5-carboxy-1-isopropylorotate sodium salt (In the formula [], Me is sodium and R ¹ is isopropyl. The same applies to the following examples.) - To 30 ml of water containing 1.5 g of monohydrate When 30 ml of carbon tetrachloride containing 0.46 g of chlorine was added dropwise at room temperature, 20 ml of gas was generated. The mixture was heated and reacted under reflux for 1 hour. After the reaction, the resulting reaction product mixture is filtered,
0.25 g (yield: 17%) of crystals of 5-chloro-1-isopropylorotic acid monohydrate was obtained. This was recrystallized from water to obtain colorless needle crystals with a decomposition point of 241-242°C. The elemental analysis values are shown below. C H N Cl Analytical value 38.30 4.34 11.09 13.80 Calculated value 38.34 4.42 11.18 14.14 (as C ₈ H ₁₁ ClN ₂ O ₅ ) Example 2 Contains 2.62 g of 5-carboxy-1-isopropylorotate sodium salt monohydrate In 50ml of water,
Add 15 ml of 1N aqueous sodium hydroxide solution, then add 7.44 mL of 12% by weight aqueous sodium hypochlorite solution.
g was added. The mixture was heated and reacted under reflux for 1 hour. After the reaction, add 1 to the resulting reaction product mixture at room temperature.
When 40ml of specified hydrochloric acid is added dropwise, the gas becomes 130ml.
ml occurred. The mixture was filtered to give 5-chloro-1
-Isopropylorotic acid monohydrate crystal 0.44
g (yield: 18%) was obtained. The liquid was concentrated under reduced pressure, and 10 ml of water was added to the residue and filtered to obtain 0.52 g (yield: 21%) of crystals of 5-chloro-1-isopropylorotic acid monohydrate. Example 3 When 10 ml of carbon tetrachloride containing 0.44 g of chlorine was added dropwise to 90 ml of water containing 1.53 g of 5-carboxy-1-phenylorotic acid sodium salt monohydrate at room temperature, 97.5 ml of gas was generated. . The mixture was allowed to react for 20 hours with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
0.38 g (yield: 26%) of crystals of 5-chloro-1-phenylorotic acid monohydrate was obtained. This was recrystallized from water to obtain colorless needle crystals with a decomposition point of 242-243°C. The elemental analysis values are shown below. C H N Cl Analytical value 46.54 3.17 9.54 12.14 Calculated value 46.41 3.19 9.84 12.45 (as C ₁₁ H ₉ ClN ₂ O ₅ ) Example 4 5-carboxy-1-(p-methoxyphenyl) orotate sodium salt 1 water To 60 ml of water containing 3.26 g of hydroxide, 15 ml of 1N aqueous sodium hydroxide solution was added at room temperature, and then 7.44 g of a 12% by weight aqueous sodium hypochlorite solution was added. The mixture was heated and reacted under reflux for 1 hour. After the reaction, add 1 to the resulting reaction product mixture at room temperature.
When 40ml of specified hydrochloric acid is added dropwise, the gas becomes 153
ml occurred. The mixture was filtered to give 5-chloro-1
-(p-methoxyphenyl)orotic acid crystals
1.54 g (yield: 52%) was obtained. This was recrystallized with ethanol to obtain pale yellow fine needle crystals with a decomposition point of 236°C. The elemental analysis values are shown below. C H N Cl Analytical value 48.97 3.12 9.42 11.68 Calculated value 48.58 3.06 9.44 11.95 (as C ₁₂ H ₉ ClN ₂ O ₅ ) Example 5 5-carboxy-1-(p-chlorophenyl)
Number of carbon tetrachloride containing 0.47 g of chlorine at room temperature in 90 ml of water containing 1.83 g of orotate sodium salt monohydrate
10 ml was added dropwise and 77.5 ml of gas evolved. The mixture was allowed to react for one day with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
0.70 g of crystals were obtained. This was added to 50 ml of ethanol, and the heated filtrate was concentrated under reduced pressure to obtain 0.42 g (yield: 25%) of crystals of 5-chloro-1-(p-chlorophenyl)orotic acid. This was recrystallized with water to obtain colorless crystals with a decomposition point of 233-234°C as a 1:1 molar adduct with water. The elemental analysis values are shown below. C H N Cl Analytical value 41.65 2.36 8.76 21.54 Calculated value 41.40 2.53 8.78 22.22 (as C ₁₁ H ₈ Cl ₂ N ₂ O ₅ ) Example 6 5-carboxy-1-(p-chlorophenyl)
To 50 ml of water containing 1.65 g of sodium orotate monohydrate was added 7.5 ml of a 1N aqueous solution of sodium hydroxide at room temperature, followed by 3.71 g of a 12% by weight aqueous solution of sodium hypochlorite. The mixture was heated and reacted under reflux for 1 hour. After the reaction, the resulting reaction product mixture was added with 2
Adding 10ml of specified hydrochloric acid dropwise produces 65ml of gas.
Occurred. The mixture was filtered to give 5-chloro-1-
0.97 g (yield: 61%) of crystals of (p-chlorophenyl)orotic acid monohydrate was obtained. Example 7 To 80 ml of water containing 2.14 g of 5-carboxy-1-isopropylorotate sodium salt monohydrate,
20 ml of carbon tetrachloride containing 1.38 g of bromine was added dropwise at room temperature, 130 ml of gas evolved. The mixture was heated and reacted at 60°C for 7 hours. After the reaction, the resulting reaction product mixture is filtered,
Crystals of 5-bromo-1-isopropylorotic acid
1.26g (yield: 56%) was obtained. This was recrystallized with acetonitrile to obtain colorless crystals to which 1/2 molecule of acetonitrile had been added with a decomposition point of 248-249°C. The elemental analysis values are shown below. C H N Br Analytical value 36.47 3.75 12.19 27.33 Calculated value 36.32 3.56 11.77 26.84 (as C ₈ H ₉ BrN ₂ O ₄・1/2CH ₃ CN) Example 8 Sodium 1-(n-butyl)-5-carboxyorotate・To 25 ml of water containing 0.74 g of monohydrate,
When 10 ml of water containing 0.43 g of bromine was added under ice cooling, 45 ml of gas was generated. The mixture was allowed to react for 20 hours with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
5-bromo-1-(n-butyl)orotic acid 1
0.29 g (yield: 35%) of hydrate crystals were obtained. This was recrystallized from water to obtain pale yellow massive crystals with a decomposition point of 218-219°C. The elemental analysis values are shown below. C H N Br Analytical value 35.08 4.03 9.05 25.92 Calculated value 34.97 4.24 9.06 25.85 (as C ₉ H ₁₃ BrN ₂ O ₅ ) The liquid was concentrated under reduced pressure, 5 ml of water was added to the residue, filtered, and further 5-bromo- 1-(n-butyl)
Orotic acid monohydrate crystal 0.1g (yield: 12%)
I got it. Example 9 When 20 ml of water containing 1.35 g of bromine was added dropwise to 100 ml of water containing 2.15 g of 1-benzyl-5-carboxyorotic acid sodium salt monohydrate under ice cooling, 360 ml of gas was generated. . The mixture was allowed to react for 5 hours with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
Crystals of 1-benzyl-5-bromoorotic acid 1.42
g (yield: 63%) was obtained. This was recrystallized with ethanol to obtain orange massive crystals with a decomposition point of 255-256°C. The elemental analysis values are shown below. C H N Br Analytical value 44.56 2.86 8.44 24.78 Calculated value 44.32 2.79 8.61 24.57 (as C ₁₂ H ₉ BrN ₂ O ₄ ) Example 10 Water containing 1.6 g of 5-carboxy-1-phenylorotic acid potassium salt monohydrate After adding 0.88 g of N-bromosuccinimide to 100 ml at room temperature, the mixture was stirred at room temperature and 320 ml of gas evolved.
The mixture was allowed to react for 1.5 hours with stirring at room temperature. After the reaction, the resulting reaction product mixture was filtered.
1 ml of concentrated sulfuric acid was added to the solution, and the separated crystals were filtered to obtain 0.22 g (yield: 13%) of crystals of 5-bromo-1-phenylorotic acid monohydrate. This was recrystallized from ethanol to obtain colorless needle crystals with a decomposition point of 260-262°C. The elemental analysis values are shown below. C H N Br Analytical value 40.33 2.73 8.35 24.51 Calculated value 40.14 2.75 8.51 24.30 (as C ₁₁ H ₉ BrN ₂ O ₅ ) Example 11 Water containing 1.48 g of 5-carboxy-1-phenyl orotinate sodium salt monohydrate 10 ml of water containing 0.94 g of bromine was added dropwise to 50 ml under ice cooling.
The mixture was allowed to react for 1 hour with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
1 g (yield: 61%) of crystals of 5-bromo-1-phenylorotic acid monohydrate was obtained. Example 12 To 30 ml of water containing 1.39 g of potassium 5-carboxy-1-(p-tolyl)orotate monohydrate, 0.81 g of N-bromosuccinimide was added at room temperature, and the mixture was stirred at room temperature. , 92ml of gas was generated. The mixture was heated and reacted under reflux for 15 minutes. After the reaction, the resulting reaction product mixture was filtered.
The liquid was concentrated under reduced pressure, and 10 ml of water was added to the residue and filtered to obtain 0.54 g (yield: 38%) of crystals of 5-bromo-1-(p-tolyl)orotic acid. This was recrystallized with ethanol to obtain colorless needle-shaped crystals with a decomposition point of 242°C as an adduct with ethanol in a molar ratio of 1:1. The elemental analysis values are shown below. C H N Br Analytical value 45.30 4.08 7.53 21.46 Calculated value 45.30 4.07 7.55 21.53 (as C ₁₄ H ₁₅ BrN ₂ O ₅ ) Example 13 5-carboxy-1-(p-tolyl) orotate potassium salt monohydrate In 50ml of water containing 0.64g,
After dropping 10 ml of water containing 0.43 g of bromine under ice cooling,
The mixture was allowed to react for 20 hours with stirring at room temperature. During this time, 35 ml of gas was generated. After the reaction, the resulting reaction product mixture is filtered,
0.19 g (yield: 29%) of crystals of 5-bromo-1-(p-tolyl)orotic acid was obtained. Example 14 When 20 ml of water containing 0.85 g of bromine is added dropwise at room temperature to 80 ml of water containing 1.74 g of 5-carboxy-1-(p-methoxyphenyl)orotate sodium salt monohydrate, a gas 58ml was generated. The mixture was allowed to react for one day with stirring at room temperature. After the reaction, the resulting reaction product mixture is filtered,
0.94 g (yield: 52%) of crystals of 5-bromo-1-(p-methoxyphenyl)orotic acid was obtained. This was recrystallized with ethanol to obtain yellow needle-like crystals with a decomposition point of 266-268°C as an adduct with ethanol in a molar ratio of 1:1. The elemental analysis values are shown below. C H N Analytical value 43.80 3.85 7.05 Calculated value 43.43 3.90 7.24 (as C ₁₄ H ₁₅ BrN ₂ O ₆ ) Example 15 5-carboxy-1-(p-chlorophenyl)
Water containing 1.33g of orotate potassium salt monohydrate
After adding 10 ml of water containing 0.63 g of bromine to 50 ml under ice cooling, the mixture was reacted for 20 hours with stirring at room temperature. During this time, 45 ml of gas was generated. After the reaction, the resulting reaction product mixture is filtered,
1.08 g (yield: 76%) of crystals of 5-bromo-1-(p-chlorophenyl)orotic acid monohydrate was obtained. This was recrystallized from water to obtain pale orange massive crystals with a decomposition point of 235-237°C. The elemental analysis values are shown below. C H N Analytical value 36.79 2.45 7.78 Calculated value 36.34 2.22 7.71 (as C ₁₁ H ₈ BrClN ₂ O ₅ ) Example 16 5-carboxy-1-(3,5-dichlorophenyl)orotate sodium salt monohydrate 1.8g
70 ml of water containing 1.09 g of bromine under cooling.
After adding ml dropwise, the mixture was stirred at room temperature.
The reaction was allowed to proceed for 18 hours. During this time, 190 ml of gas was generated. After the reaction, the resulting reaction product mixture is filtered,
5-bromo-1-(3,5-dichlorophenyl)
1.98 g (yield: 76%) of orotic acid crystals were obtained.
This is recrystallized with ethanol to form an adduct with a molar ratio of 1:1, which has a decomposition point of 230 to 232℃.
Colorless needle-like crystals were obtained. The elemental analysis values are shown below. C H N Analytical value 36.27 2.44 6.51 Calculated value 36.65 2.60 6.58 (as C ₁₃ H ₁₁ BrCl ₂ N ₂ O ₅ ) Example 17 Water containing 1.31 g of 5-carboxy-1-isopropylorotate sodium salt monohydrate to 50ml,
17.5 ml of 1N aqueous solution of sodium hydroxide at room temperature
was added, and then 1.27 g of iodine was added. The mixture was heated and reacted under reflux for 2.5 hours. After the reaction, 10 ml of 2N hydrochloric acid was added to the resulting reaction product mixture and filtered to obtain 0.79 g of crystals of 5-iodo-1-isopropylorotic acid (yield: 49%).
I got it. This is recrystallized with ethanol to form an adduct with a molar ratio of 1:1 and the decomposition point
Colorless needle crystals were obtained at 242-244°C. The elemental analysis values are shown below. C H N Analytical value 32.63 4.02 7.72 Calculated value 32.44 4.08 7.57 (as C ₁₀ H ₁₅ IN ₂ O ₅ ) Example 18 5-bis(ethoxycarbonyl)methylene-3
- After adding 3.68 g of cyclohexylhydantoin to 44 ml of 1N aqueous solution of sodium hydroxide, the mixture was heated and reacted under reflux for 1 hour. After the reaction, add 2.76 iodine to the reaction mixture under ice cooling.
After adding g, the mixture was heated again and reacted under reflux for 4 hours. The resulting reaction product mixture was filtered, and 4 ml of concentrated hydrochloric acid was added to the liquid at room temperature.
88%). This was recrystallized with ethanol,
As an adduct with ethanol in a molar ratio of 1:1, pale yellow microacicular crystals with a decomposition point of 239-240°C were obtained. The elemental analysis values are shown below. C H N Analytical value 38.08 4.67 6.81 Calculated value 38.06 4.67 6.83 (as C ₁₃ H ₁₉ IN ₂ O ₅ ) Example 19 3-allyl-5-bis(ethoxycarbonyl)
After adding 14 ml of a 1N aqueous solution of sodium hydroxide at room temperature to 16 ml of water containing 1.1 g of methylenehydantoin, the mixture was heated and reacted under reflux for 1 hour. After the reaction, the resulting reaction product mixture was cooled with ice,
After adding 0.94 g of iodine, the mixture was heated and reacted under reflux for 4 hours. After the reaction, add 1.5 ml of concentrated hydrochloric acid to the reaction product mixture at room temperature.
ml and filtered to obtain 0.65 g of crystals of 1-allyl-5-iodoorotic acid 1/2 hydrate (yield: 53%)
I got it. Recrystallize this with 15 ml of water to find the decomposition point.
Yellow needle-shaped crystals were obtained at 185-186°C. The elemental analysis values are shown below. C H N Analytical value 29.12 2.42 8.43 Calculated value 29.02 2.44 8.46 (as C ₈ H ₇ IN ₂ O ₄・1/2H ₂ O) Example 20 5-carboxy-1-phenylorotic acid sodium salt monohydrate 1.5 g Add 0.2 g of sodium hydroxide to 50 ml of water containing iodine at room temperature, then add iodine.
After adding 1.29 g, the mixture was heated and reacted under reflux for 4 hours. After the reaction, 0.5 ml of concentrated hydrochloric acid was added to the resulting reaction product mixture at room temperature and filtered to obtain 1.71 g (yield: 94%) of crystals of 5-iodo-1-phenyl orotic acid. This is recrystallized with ethanol to produce an adduct with a molar ratio of 1:1, with a decomposition point of 258
Colorless needle crystals at ~260°C were obtained. The elemental analysis values are shown below. C H N I Analytical value 38.87 3.24 6.99 31.65 Calculated value 38.63 3.24 6.93 31.40 (as C ₁₃ H ₁₃ IN ₂ O ₅ ) Example 21 5-bis(ethoxycarbonyl)methylene-3
- After adding 80 ml of a 1N aqueous solution of sodium hydroxide to 6.65 g of phenylhydantoin at room temperature, the mixture was heated and reacted under reflux for 1 hour. After the reaction, 5.08 g of iodine was added to the resulting reaction product mixture at room temperature. The mixture was heated and reacted under reflux for 4.5 hours. After the reaction, the reaction mixture was cooled to room temperature and filtered. 40 ml of 2N hydrochloric acid was added to the solution and filtered to obtain 6.92 g (yield: 97%) of crystals of 5-iodo-1-phenylorotic acid. Example 22 5-bis(ethoxycarbonyl)methylene-3
-(p-methoxyphenyl)hydantoin 3.62g
After adding 40 ml of a 1N aqueous solution of sodium hydroxide at room temperature to 20 ml of water containing
The reaction was carried out under reflux for 1 hour. After the reaction, add 2.54 g of iodine to the reaction mixture at room temperature.
was added, the mixture was heated and reacted under reflux for 3 hours. After the reaction, the reaction product mixture was allowed to cool to room temperature and was filtered, and 20 ml of 2N hydrochloric acid was added to the solution, crystals precipitated and 80 ml of gas was generated. The mixture was filtered to give 5-iodo-1-(p-methoxyphenyl).
3.3 g (yield: 85%) of orotic acid crystals were obtained.
This was recrystallized with ethanol to obtain yellow needle-like crystals with a decomposition point of 263°C as an adduct with ethanol in a molar ratio of 1:1. The elemental analysis values are shown below. C H N Analytical value 39.05 3.52 6.26 Calculated value 38.73 3.48 6.45 (as C ₁₄ H ₁₅ IN ₂ O ₆ ) Example 23 5-carboxy-1-(p-chlorophenyl)
To 50 ml of water containing 1.65 g of orotate sodium salt monohydrate was added 17.5 ml of a 1N aqueous solution of sodium hydroxide at room temperature, followed by 1.27 g of iodine, and the mixture was heated to reflux. The reaction was allowed to proceed for 7 hours. After the reaction, the reaction product mixture was cooled to room temperature and filtered, and 10 ml of 2N hydrochloric acid was added to the solution to separate crystals. After this, 1.57 g of crystals of 1-(p-chlorophenyl)-5-iodoorotic acid
(yield: 80%). This was recrystallized with ethanol to obtain yellow fine needle crystals with a decomposition point of 268-270°C. The elemental analysis values are shown below. C H N Analytical value 33.00 1.93 7.18 Calculated value 33.66 1.54 7.14 (as C ₁₁ H ₆ ClIN ₂ O ₄ ) Example 24 5-bis(ethoxycarbonyl)methylene-3
-(p-chlorophenyl)hydantoin 7.34g
, a 1N aqueous solution of sodium hydroxide at room temperature80
ml, the mixture was heated and reacted under reflux for 1 hour. After the reaction, add 5.08 g of iodine to the reaction mixture at room temperature.
was added and the mixture was heated again and reacted under reflux for 5 hours. After the reaction, the reaction product mixture was cooled to room temperature and filtered. When 40 ml of 2N hydrochloric acid was added, crystals were separated. Through this process, crystals of 1-(p-chlorophenyl)-5-iodoorotic acid6.73
g (yield: 86%) was obtained. Next, in order to demonstrate that the 5-haloorotic acids of this invention are useful as agricultural and horticultural fungicides,
The following reference example is shown. In the reference examples, parts indicate parts by weight. Reference example (1) Preparation of test emulsion 20 parts of 5-haloorotic acid, 5 parts of toxanone,
75 parts of xylene was mixed to obtain 100 parts of an emulsion. (2) Control test against powdery mildew in cucumbers Grow cucumbers (variety: Sagami half-day knots) in synthetic resin pots with a diameter of 6 cm, one plant per pot, sow cucumber seeds, and grow seedlings on the 17th day. , an emulsion prepared by the above method (when used, diluted with water to
-The concentration of haloorotic acid was set to 1000ppm. )
was scattered. After air-drying, each seedling was treated with a suspension of Sphaerotheca fuliginea (conidia dropped into a Petri dish with a soft brush from the leaf surface of infected leaves of Sphaerotheca fuliginea) with distilled water under an optical microscope. per field of view (magnification: 150x)
A spore suspension prepared to have 10 spores was uniformly inoculated by spraying. After inoculation, the seedlings were left in an isolated glass greenhouse, and on the 11th day, the number of lesions of cucumber powdery mildew that appeared on the first true leaves was investigated.
The control rate of 5-haloorotic acid was calculated using the following calculation method. The results are shown in Table 1 as a control effect index. Control rate (%) = (1 - average number of lesions in treated area / average number of lesions in untreated area)
×100 Control effectiveness index control rate (%) 5 91-100 4 81-90 3 61-80

【table】

[Table] * Control drug

Claims (1)

[Claims] 1 formula [In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an allyl group, a cyclohexyl group, a benzyl group, or [Formula] (wherein, R ² is a methyl group, a methoxy group, or a halogen atom, and n is 0, 1 or 2), and X represents chlorine, bromine or iodine]
Haloorotic acids. 2 formulas [In the formula, Me represents an alkali metal, and R ¹ is an alkyl group having 1 to 4 carbon atoms, an allyl group, a cyclohexyl group, a benzyl group, or [Formula] (wherein, R ² is a methyl group, a methoxy group, or a halogen atom. and n is 0, 1 or 2) is reacted with a halogenating agent. [In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an allyl group, a cyclohexyl group, a benzyl group, or [Formula] (wherein, R ² is a methyl group, a methoxy group, or a halogen atom, and n is 0, 1 or 2), and X represents chlorine, bromine or iodine.